LIBRARY 

OF  THE 

UNIVERSITY  OF  CALIFORNIA. 

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Class 


The  Fractionation   of  Crude 

Petroleum  by  Capillary 

Filtration. 


DISSERTATION 


SUBMITTED   TO   THE   BOARD   OF   UNIVERSITY  STUDIES   OF 

THE  JOHNS   HOPKINS   UNIVERSITY  IN  CONFORMITY 

WITH  THE  REQUIREMENTS  FOR  THE  DEGREE 

OF  DOCTOR  OF  PHILOSOPHY. 


BY 


MARSHALL   PERLEY  CRAM, 


EASTON,  PA.  : 

ESCHENBACH  PRINTING  COMPANY. 
1908 


The  Fractionation   of  Crude 

Petroleum  by  Capillary 

Filtration. 


DISSERTATION 


SUBMITTED   TO   THE   BOARD   OF  UNIVERSITY  STUDIES   OF 

THE  JOHNS   HOPKINS   UNIVERSITY  IN  CONFORMITY 

WITH  THE  REQUIREMENTS  FOR  THE  DEGREE 

OF  DOCTOR  OF  PHILOSOPHY. 


BY 


MARSHALL  PERLEY  CRAM. 


1908 


EASTON,  PA.  : 

ESCHENBACH  PRINTING  COMPANY. 
1908 


CONTENTS. 


Page. 

Acknowledgment 4 

The  Fractionation  of  Crude  Petroleum 5 

Water  Fractionation 45 

Oil  Lost  in  the  Earth 47 

Fractionating  Power  of  Substances  other  than  Fuller's  Earth  .   .  49 

Summary 50 

Biographical 51 


202452 


ACKNOWLEDGMENT. 


The  author  takes  pleasure  in  expressing  his  gratitude 
to  President  Remsen,  Professor  Morse,  and  Professor  Jones 
for  instruction  in  the  lecture  room  and  laboratory.  Especial 
thanks  are  due  to  Dr.  Gilpin,  under  whose  personal  direction 
this  investigation  has  been  pursued,  and  to  Dr.  D.  T.  Day, 
of  the  U.  S.  G.  S.,  who  has  contributed  valuable  suggestions 
and  apparatus. 


The  Fractionation  of  Crude  Petroleum 
by  Capillary  Filtration. 


When  in  process  of  refinement,  black  vaseline  is  filtered 
through  warm  dry  fuller's  earth  the  first  product  is  an  oil 
perfectly  liquid  at  ordinary  temperatures,  while  the  suc- 
ceeding portions  are  progressively  more  viscous  until  quite 
hard  vaseline  is  obtained.  This  observation,  that  a  frac- 
tional separation  of  oils  in  vaseline  had  been  effected,  sug- 
gested to  D.  T.  Day  that  a  like  result  might  be  obtained 
with  crude  petroleum.  He  applied  this  method  to  a  sample 
of  the  green  crude  petroleum  from  the  "third  sand,"  Venango 
County,  Pennsylvania,  and  found  that  light  products,  chiefly 
gasoline,  first  appeared  when  such  crude  oil  was  allowed 
to  filter  down  through  a  long  glass  tube  filled  with  granu- 
lated or  powdered  fuller's  earth.1 

Following  this  a  more  elaborate  system  of  specially  con- 
structed funnels  similar  to  those  used  by  the  refiners  of 
vaseline  in  testing  the  comparative  value  of  various  fuller's 
earths  was  used.  The  results  from  this  were  briefly  sum- 
marized in  a  paper  upon  the  ability  of  petroleum  to  migrate 
in  the  earth.2  Engler  later  verified  these  results  and  showed 
that  the  separation  was  mechanical  and  that  no  oxidation 
was  effected  in  the  process.  Day  next  used  a  large  closed 
funnel  of  galvanized  iron  holding  about  one  hundred  pounds 
of  fuller's  earth.  When  crude  petroleum  was  dropped 
slowly  and  regularly  into  this,  quite  light  oils  at  first,  fol- 
lowed by  the  usual  succession  of  heavier  oils,  were  obtained. 
As  it  was  evident  from  this  work  that  much  of  the  oil  passed 
through  crevices  without  any  change  he  tried  the  effect 
of  reversing  the  route  of  the  oil  and  of  allowing  it  to  diffuse 

1  Philadelphia  Acad.  of  Sci.,  1897. 

2  Trans.  Petroleum  Congress  (Paris),  1900. 


upward  through  a  tube  packed  tightly  with  fuller's  earth. 
In  such  a  tube  the  lighter  constituents  rose  much  more 
rapidly  than  the  more  viscous  oils  so  that  by  separating 
the  fuller's  earth  from  different  sections  of  the  tube  and 
displacing  the  oil  by  water,  quite  different  oils  were  obtained 
from  the  upper  and  lower  parts  of  the  tube. 

By  using  several  tubes  and  uniting  oils  of  the  same  specific 
gravity,  oil  of  different  grades  could  be  collected  in  sufficient 
quantity  to  be  fractionated  again,  and  the  process  con- 
tinued until  oils  result  which  are  not  altered  by  further 
passage  through  tubes  filled  with  fuller's  earth.  At  the 
suggestion  and  with  the  cooperation  of  Day,  we  have  taken 
up  this  problem  with  the  results  here  stated. 

The  tubes  used  first  were  three  feet  long  and  one  and 
one-eighth  inches  in  diameter.  They  were  closed  at  the 
lower  end  with  corks,  along  the  sides  of  which  grooves  had 
been  cut,  the  top  of  the  cork  being  covered  with  a  bit  of 
cotton  cloth  to  prevent  the  earth  from  sifting  out  of  the 
grooves.  Such  tubes  filled  with  fuller's  earth1  were  placed 
with  their  lower  ends  in  an  open  dish  of  petroleum  and  the 
oil  was  allowed  to  rise. 

At  room  temperatures  (i8°-22°  C.)  and  atmospheric  pres- 
sure, the  rate  of  rise  of  crude  petroleum  in  a  tube  filled  with 
fuller's  earth  was  very  slow.  In  seven  days  the  oil  ascended 
but  73  cm.  in  one  tube,  while  ten  days  in  one  case  and  seven 
in  another  were  required  for  it  to  rise  59  cm.  To  study  the 
effect  of  heat,  a  glass  tube  about  three  feet  long  and  iV8 
inches  in  diameter,  was  filled  with  earth  and  placed  in  a 
bottle  holding  about  two  liters  of  oil,  and  the  whole  heated 
by  an  electric  stove  with  which  temperatures  considerably 
above  those  of  the  room  could  be  maintained  day  and  night. 
The  temperature  of  the  tube  was  kept  between  40°  and 
70°  for  three  days,  in  which  time  the  oil  rose  54.7  cm.  in 
the  tube;  in  another  tube  packed  in  all  ways  like  the  former 
but  held  at  room  temperature  (about  20°),  the  oil  rose 
46  cm.  in  the  same  length  of  time.  With  two  tubes  in  which 
the  earth  was  packed  much  less  compactly,  the  time  required 
for  the  oil  to  rise  54  cm.  was  four  days  for  the  tube  at  room 

1  The  fuller's  earth  used  in  this  work  was  kindly  furnished  by  the 
Atlantic  Refining  Co.,  of  Philadelphia. 


temperature    and   two   days    for    the   one    at    50°    to    80°. 

The  rate  of  rise  evidently  was  but  little  effected  by  heat, 
at  least  within  this  range  of  temperature,  and  higher  tem- 
peratures could  not  be  used  without  loss  of  the  more  volatile 
constituents  of  the  oil. 

The  next  attempt  at  increasing  the  rate  of  rise  of  the  oil 
consisted  in  applying  diminished  pressure  to  the  top  of  the 
tube  which  reduced  the  time  required  for  the  oil  to  reach  the 
top  of  a  tube  five  feet  long  from  several  weeks  to  seventeen 
hours.  If  diminished  pressure  is  continued  after  the  oil  has 
reached  the  top,  provided  the  oil  is  not  exhausted  in  the 
reservoir  at  the  bottom,  oil  will  be  drawn  over  from  the  top 
of  the  tube.  The  specific  gravity  of  the  oil  thus  collected 
steadily  rises  as  it  comes  over.  The  samples  so  obtained, 
however,  stand  under  very  low  pressures  for  some  time, 
which  may  cause  a  loss  of  their  more  volatile  constituents. 
This  suggested  applying  increased  pressure  to  the  oil  in  the 
reservoir  rather  than  diminished  pressure  to  the  top  of  the 
tube,  and  an  iron  bomb,  like  those  used  for  the  transporta- 
tion of  mercury,  was  fitted  with  an  iron  pipe  seven  feet  long 
to  contain  earth  and  a  side  arm  at  the  bottom  of  the  bomb 
to  which  a  water  column  might  be  attached. 

The  bomb  which  held  about  two  liters  could  be  partly 
filled  with  petroleum  and  the  pipe  containing  the  earth 
screwed  into  the  top.  The  side  arm  which  opened  into  the 
bottom  of  the  bomb  could  then  be  connected  with  the  water 
pressure  so  that  the  lower  part  of  the  bomb  was  filled  with 
water  which  drove  the  petroleum  upwards.  The  oil  ob- 
tained at  the  top,  however,  was  fractionated  no  further  nor 
in  any  larger  amounts  than  when  the  oil  was  not  allowed  to 
emerge  from  the  top  of  the  tube.  The  difficulty  of  setting 
up  such  a  pressure  apparatus  with  tight  connections,  as 
well  as  the  range  of  pressure  required — a  column  of  water 
seven  feet  high  being  too  great  when  the  oil  was  just  started 
up  the  tube  while  a  column  thirty  feet  high  was  insufficient 
when  it  was  near  the  top — made  its  use  impracticable. 

To  use  diminished  pressure,  the  earth  in  the  tubes  must 
not  be  packed  so  hard  that  the  air  just  above  the  oil  cannot 


8 

be  drawn  through  the  earth  above,  nor  must  the  earth  be 
packed  so  loosely  that  the  oil  will  rise  as  in  a  vacuum.  The 
right  degree  of  hardness  is  obtained  by  filling  about  a  foot 
of  the  tube  at  a  time  and  packing  that  much  earth  as  hard 
as  possible  with  a  wooden  rod  tipped  with  a  rubber  stopper. 
If  the  tube  when  pounded  upon  the  floor,  rings  in  the  hand, 
the  earth  is  apt  to  be  packed  too  closely.  Packing  tubes 
may  be  much  facilitated  by  filling  several  at  once  with  a 
separate  ramrod  for  each.  By  allowing  a  few  minutes  to 
elapse  between  successive  liftings  of  the  ramrod,  much  labor 
is  avoided. 

The  fuller's  earth  was  first  heated  in  shallow  iron  pans 
until  it  ceased  to  form  geysers  when  stirred.  The  earth 
must  be  thoroughly  cold  before  it  is  packed  into  tubes  or  the 
contraction  is  sufficient  to  allow  the  oil  to  run  up  the  tube 
immediately  when  the  air  is  exhausted. 

The  lower  end  of  the  tube  is  best  closed  with  a  cork  with 
six  or  seven  grooves  cut  along  the  side,  and  the  inner  end 
covered  with  a  bit  of  cloth  to  keep  the  earth  from  sifting 
out  of  the  grooves.  At  the  top  of  the  tube  a  bit  of  cotton 
waste  below  a  rubber  stopper  will  prevent  any  earth  from 
being  drawn  up  when  the  air  is  exhausted. 

The  tubes  used  first  were  three  feet  long  and  one  and  one- 
eighth  inches  in  diameter  and  of  glass.  Much  trouble  was 
experienced  on  account  of  their  breaking,  not  when  in  ser- 
vice, but  soon  after  they  had  been  used.  This  was  thought 
to  be  due  to  the  age  of  the  tubing,  but  the  same  happened 
with  new  tubes  five  feet  long  and  one  and  one-fourth  inches 
in  diameter.  With  the  idea  that  the  iron  scraper  used  to 
remove  the  earth  from  the  tubes  might  be  the  cause,  a  scraper 
entirely  of  wood  was  tried,  but  this  did  not  decrease  the 
breakage,  it  being  nothing  unusual  on  going  to  the  laboratory 
in  the  morning  to  find  half  of  the  tubes  which  had  been 
emptied  the  day  before  cracked. 

It  had  been  considered  necessary  to  use  tubes  of  glass  in 
order  that  the  height  to  which  the  oil  had  risen  could  be 
seen  and  that  in  removing  the  oil  from  the  middle  of  the  tube 
it  might  be  scraped  out  to  a  sharp  dividing  line,  since  the 


level  to  which  the  oil  has  risen  is  the  point  from  which  all 
measurements  should  be  made  of  sections  into  which  the  tube 
is  to  be  divided.  Tin  tubes  were  used  later  to  avoid  the 
trouble  experienced  with  glass  tubes.  These  tin  tubes  were 
emptied  by  shaking  the  earth  from  the  bottom  into  four 
thirty  centimeter  cylinders  of  the  same  diameter  as  the  tube, 
these  cylinders  being  made  of  two  curved  pieces  of  tin  held 
together  by  a  cap  at  one  end  and  a  ring  at  the  other.  The 
cylinders  containing  the  contents  of  the  tube  could  be  opened 
lengthwise  and  the  earth  divided  into  any  desired  lengths. 
Two  glass  tubes  five  feet  long  and  one  and  one-fourth  inches 
in  diameter  were  set  up  in  the  same  dish  of  petroleum  with 
ten  or  twenty  tin  tubes  five  and  one-half  feet  long  and  of  the 
same  diameter,  and  when  the  oil  stood  at  the  top  of  the 
glass  tubes  the  tin  ones  were  also  opened.  Glass  tubes,  of 
course,  can  be  emptied  as  well  as  tin  ones  by  shaking  the 
contents  from  the  bottom,  and  no  more  tubes  broke  after 
this  method  was  adopted. 

The  level  to  which  the  oil  will  rise  can  be  regulated  by  the 
amount  of  oil  in  which  the  tube  is  placed,  and  in  the  later 
work  the  adoption  of  this  method  did  away  with  the  use  of 
glass  tubes  entirely.  950  cc.  of  oil  in  a  tube  one  and  one- 
fourth  inches  in  diameter  and  five  and  one- half  feet  long  will 
rise  to  within  20  to  35  cm.  of  the  top. 

When  the  oily  earth  has  been  removed  from  the  tube, 
the  oil  may  be  separated  by  adding  water.  As  first  prac- 
tised, enough  water  was  added  to  form  a  very  thin  mud  which 
was  thoroughly  stirred  by  a  small  propeller  driven  by  a 
water  motor.  The  mixed  earth,  oil,  and  water  were  then 
poured  into  a  large  separating  funnel  and  allowed  to  stand 
several  minutes  until  the  oil  had  collected  at  the  top.  The 
earth  and  water  could  then  be  drawn  off  and  the  pure  oil  left. 

It  was  found  later,  however,  that  if  less  water  is  added  to 
the  earth  as  removed  from  the  tubes,  after  standing  a  few 
minutes  all  the  water  will  pass  into  the  earth  and  this  will  be 
accompanied  by  the  liberation  of  oil.  Oil  so  liberated  can 
then  be  poured  off  directly  from  the  earth  without  the  labor 
of  churning.  When  water  first  begins  to  liberate  oil,  the 


10 

earth  is  granular  while  when  more  water  has  been  added  and 
the  last  of  the  oil  recovered  the  earth  has  the  consistency 
of  a  thin  paste  which  will  flow  when  the  dish  is  inclined, 
which  it  will  not  do  when  the  oil  begins  to  come  off. 

All  the  oil  from  the  same  section  of  a  tube  is  of  the  same 
color  irrespective  of  whether  it  is  the  first  oil  to  come  off 
when  water  is  added  or  whether  it  does  not  come  until  the 
last.  It  was  assumed  at  first  that  all  such  oil  which  came 
from  the  same  section  of  earth  had  the  same  specific  gravity 
irrespective  of  whether  it  was  the  first  or  last  replaced  when 
water  was  added,  but  this  was  found  later  not  to  be  the  case. 

The  first  oil  to  be  collected,  if  taken  in  sufficiently  small 
volume,  is  slightly  heavier  than  the  next  portion.  If  too 
much  is  included  in  the  first  sample  this  will  not  be  the  case. 
Beginning  with  the  second  sample  the  successive  portions 
of  oil  steadily  increase  in  specific  gravity,  this  gradual  addi- 
tion of  water  affording  another  means  of  fractionation  in 
addition  to  the  separating  power  of  the  earth.  Both  of  these 
methods  of  separation  have  been  combined  in  this  investiga- 
tion. The  earth  must  be  thoroughly  mixed  after  each 
addition  of  water  to  prevent  a  layer  of  water  wet  earth  from 
isolating  earth,  which  contains  oil,  from  the  water  added. 

The  petroleum  used  was  a  dark  green  oil  from  Venango 
County,  Pennsylvania,  of  specific  gravity  0.810.  When 
950  cc.  of  this  were  drawn  upwards  in  a  tin  tube  five  and  one- 
half  feet  long  the  following  separation  was  obtained  as  shown 
in  Table  I. 


II 
TABLE  I. — SINGLE  TUBES   IN  THE   CRUDE   PETROLEUM. 

(0  (2)  (3) 

Time  required 23 . 5  hrs.  17.5  hrs.  17.5  hrs. 

Distance  from  top  of  tube 

to  oil  when  opened 31  cm.  28  cm.  28  cm. 

Sp.gr.           cc.  Sp.gr.           cc.  Sp.gr.           cc. 

A,  8  cm.  at  top 0.796       42  0.8012     30  0.8022     18 

B,  next  8  cm 0.808       45  0.804       37  0.803       35 

C,  next  18 cm 0.8125     75  0.807       47  0.8075     66 

0.8137     24  0.809       22  0.810       25 

D,  next  30  cm 0.815     130  0.8125  148  0.812     140 

E,  next  35  cm 0.818     170  0.8185   190  0.8175  145 

F,  rest 0.8205  125  0.823     100  0.821     105 


611  574  534 

The  oil  from  section  C  was  collected  in  two  portions,  the 
second  being  obtained  by  the  addition  of  more  water  after 
the  first  lot  of  oil  was  poured  off.  Although  950  cc.  of  crude 
petroleum  were  used  in  each  case,  it  will  be  noticed  that  the 
oil  recovered  measures  much  less  than  that.  When  several 
tubes  were  worked  up  together  in  one  case  9070  cc.  of  crude 
petroleum  yielded  5951  cc.  of  oil,  and  in  another  case  8915 
cc.  gave  5415  cc. 

To  collect  a  sufficient  quantity  of  oil  several  tubes  were 
placed  in  the  same  container  of  petroleum,  two  of  the  tubes 
being  of  glass  and  the  rest  of  tin.  When  the  oil  had  reached 
the  top  of  the  glass  tubes  they  and  the  tin  ones  were  opened, 
and  the  earth  from  the  same  level  in  all  the  tubes  mixed  in 
tin  pails.  The  oil  was  then  liberated  in  several  successive 
fractions  by  the  addition  of  successive  amounts  of  water. 
If  the  earth  had  been  thoroughly  mixed  after  each  addition 
of  water  the  various  oils  from  the  same  lot  of  earth  would 
increase  regularly  in  specific  gravity,  instead  of  showing  the 
variations  which  in  many  cases  they  do,  e.  g.,  the  first  oil 
to  be  displaced  by  water  in  D  and  B  of  (4),  in  Table  II,  with 
so  large  volume,  would  not  have  been  heavier  than  the 
succeeding  oils  if  the  water  and  earth  had  been  thoroughly 
mixed  before  the  oil  was  poured  off.  If  we  were  to  repeat 
the  work  instead  of  using  one  common  reservoir  for  all  the 


12 

tubes,  we  would  use  a  separate  reservoir  for  each  tube,  and 
open  the  tube  when  the  oil  in  .the  reservoir  was  exhausted. 
This  would  do  away  with  the  use  of  glass  tubes  entirely, 
besides  insuring  that  the  level  of  the  oil  in  each  tube  when 
opened  would  be  practically  the  same.  If  a  common  reser- 
voir is  to  be  used  the  tubes  should  all  be  packed  with  prac- 
tically the  same  degree  of  hardness  if  the  oil  is  to  ascend  in 
all  with  equal  rapidity  since  the  ascent  in  all  tubes  is  checked 
at  the  same  time,  i.  e.,  when  the  oil  in  the  reservoir  is  ex- 
hausted. 

Diminished  pressure  was  obtained  by  use  of  a  Chapman 
water  pump  which  reduced  the  pressure  to  from  five  to 
twelve  cm.  Hg  when  connected  with  a  system  of  tubes. 
In  the  earlier  work  the  pump  was  not  run  through  the  night, 
which  is  the  reason  for  the  much  longer  time  required  for 
these  lots  of  tubes. 

The  earth  from  a  tube  was  divided  into  six  sections,  the 
level  to  which  the  oil  had  ascended  in  the  tube  being  taken  as 
the  point  to  be  measured  from.  A,  the  top  section,  in- 
cludes the  eight  cm.  next  the  top;  B,  the  next  eight  cm.; 
C,  the  next  eighteen;  D,  the  next  thirty;  B,  the  next  thirty- 
five;  while  F  includes  what  earth  is  left.  F  varies  of  course 
depending  upon  the  height  to  which  the  oil  has  risen.  In 
fractionating  the  crude  petroleum  in  bulk,  F  was  usually 
discarded  since  it  was  so  viscous  that  it  was  deemed  im- 
possible to  pass  it  through  earth  again.  Records  from 
several  lots  of  tubes  are  given  in  Table  II.  The  specific 
gravity  was  measured  with  a  Westphal  balance,  the  oil  being 
in  every  case  at  exactly  20°  C.  While  the  fourth  decimal 
place  is  not  to  be  taken  as  strictly  accurate,  yet  it  is  con- 
sidered worth  while  to  record  it  as  giving  a  nearer  approach 
to  the  truth  than  would  result  from  the  use  of  only  three 
decimal  places. 


TABLE   II.  —  FIRST   FRACTION  ATION   OF   CRUDE 

(4)                              (5) 
Tubes                  2  glass,  8  tin.               2  glass,  7  tin. 
Distance  from          Glass,  o,  15.                   Glass,  0,6.  5. 
level  of  oil  to          Tin,  40,  15,  24,                Tin,  26,  28,  18, 
top  of  tube  in          22,  28,  19,  24,               15,  28,  12,  24. 
cm.1                           32. 
Hrs.  required                     54                                   24 

PETROLEUM. 

(6) 
2  glass,  8  tin. 
Glass,  o,  12. 
Tin,  30,  28, 
22,  30,  13,  12. 

54 

Sp.  gr. 

cc. 

Sp.  gr. 

cc. 

Sp.  gr. 

cc. 

A 

0 

.8015 

50 

0 

804 

IOO 

O 

805 

65 

0 

.8005 

350 

0, 

8055 

190 

0 

805 

20O 

B 

0 

.807 

260 

0. 

8085 

22O 

0 

807 

I4O 

O 

.810 

190 

o 

,8ll 

1  2O 

o 

8097 

125 

C 

0 

.809 

IOO 

0 

8097 

430 

0 

810 

390 

0 

.809 

400 

o 

8l22 

300 

o 

8135 

380 

o 

.810 

225 

o 

.8115 

260 

D 

0 

.815 

425 

0 

8l3 

530 

0 

8133 

610 

o 

.8145 

625 

0, 

8135 

600 

0 

816 

325 

0 

.8175 

460 

o 

816 

200 

o 

8175 

435 

o 

.825 

125 

E 

o 

.8l6 

440 

o. 

8162 

480 

o 

,816 

850 

o 

-8I5 

400 

o 

8162 

725 

o 

8195 

260 

o 

.821 

830 

o 

819 

390 

o 

.821 

330 

0 

.827 

325 

1  The  glass 

tubes  are 

five  feet 

long,  the 

tin  tubes 

five  and 

one-half 

feet.     Both  are 

one  and  one-quarter 

inches  in 

diameter. 

(7) 
2  glass,  7  tin. 
Glass,  o,  7. 
Tin  25.  26. 

23,  26,  28,  20,  28, 

TABLE  II.  (Continued). 

(8)            (9) 
2  glass,  7  tin.       2  glass,  7  tin. 
Glass,  o,  5.         Glass,  8,  5,  15. 
Tin,  16.  34,          Tin  58,  31, 
28,  15,  18,  23,  10.       60,  40,  16,  53,  16. 

do) 

2  glass,  9  tin. 
Glass,  o,  8.  5. 
Tin,  40,  32,  36,  26, 
27,  27,  20,  25,  18, 

84 

\ 

48 

117 

84 

Ao 

800 

200 

O. 

798 

130 

0 

.8025 

175 

0. 

7995 

200 

0 

.802 

H5 

O. 

80  1 

130 

o 

.8037 

I2O 

O. 

8037 

160 

0. 

806 

23 

Bo 

.8042 

2OO 

O. 

803 

155 

0 

.8042 

180 

o. 

8085 

125 

0 

.8048 

2OO 

0. 

8045 

230 

0 

.8078 

215 

0. 

810 

275 

o. 

8112 

23 

C  o 

,808 

330 

o. 

8072 

430 

o 

.809 

300 

0. 

810 

350 

0 

.8078 

430 

0. 

808 

275 

0 

.8095 

440 

0. 

812 

525 

0 

.811 

95 

o. 

808 

225 

0 

.8127 

100 

o. 

8i35 

150 

Do 

.812 

425 

0. 

8117 

420 

0 

.812 

390 

0. 

8148 

440 

o 

.812 

625 

o. 

812 

580 

o 

•8137 

400 

0. 

8i75 

700 

0 

.814 

360 

0. 

822 

2501 

0 

.8145 

300 

0. 

817 

370 

0. 

8145 

300 

0 

.8155 

200 

0. 

817 

200 

0. 

8177 

42 

Bo 

.8172 

240 

0. 

8135 

390 

0 

.818 

340 

0. 

8197 

315 

0 

.816 

650 

o. 

814 

560 

0 

•  8197 

240 

0. 

8215 

720 

o 

.8162 

660 

o. 

8248 

3901 

0 

.818 

290 

o. 

8223 

570 

0 

.8195 

300 

0. 

817 

230 

0 

.818 

350 

o. 

821 

215 

0. 

821 

42 

1  These  fractions  stood  uncovered  on  top  of  the  earth  over  night  and 
consequently  were  exposed  to  considerable  evaporation. 


^EHBLAXf^ 

C\f    TH' 


v    a 


TABLE  II.  (Continued). 


(n) 
2  glass,  8  tin. 
Glass,  o,  4. 
Tin,  o,  o, 

o,  o,  20,  17,  7i  5- 

( 
2  glass, 
Glass, 
Tin, 

19,  32,  ?5, 

12) 
6  tin. 

7,  13. 
32, 
48,  29. 

2  glass,  9  tin. 
Glass,  2,  2,  5, 
Tin,  17,  10,  n,  22, 
16,  29,  8,  5,  5,  5,  14. 

Tin 

(14) 
2  glass,  9  tin. 
Glass,  o,  o. 
,  20,  20,  5,  13,  5, 
,  5,  19,  8,  12,  14. 

39 

60 

20 

16.5 

Ao 

•799 

80 

0 

.798 

150 

0 

•8oi5 

no 

0 

798 

225 

0 

.802 

1  80 

O 

.801 

140 

0 

•8055 

40 

o  .  8005 

no 

O 

.8028 

125 

O 

8015 

80 

0 

•8033 

100 

Bo 

:8o7 

200 

O 

.8022 

1  60 

0 

.802 

230 

0. 

80I5 

210 

0 

.8115 

140 

0 

.806 

105 

0 

.8072 

60 

O 

804 

150 

0 

.8072 

20 

0 

.8085 

50 

0. 

8058 

1  2O 

o 

.8075 

75 

C  o 

.810 

300 

o 

807 

40O 

o 

.806 

340 

O. 

8048 

500 

o 

.811 

490 

0 

809 

200 

o 

.808 

220 

0. 

8065 

385 

o 

.8145 

175 

0 

8115 

60 

0 

.8072 

320 

0. 

8075 

225 

o 

.8097 

150 

D  o 

8i33 

450 

0. 

811 

400 

0 

.809 

400 

0. 

810 

500 

0 

8133 

530 

o. 

8097 

42O 

0 

.8135 

250 

O. 

810 

660 

0. 

816 

290 

o. 

811 

290 

0 

.8115 

680 

O. 

810 

650 

0. 

8142 

250 

0. 

815 

60 

0.812 

650 

0. 

812 

260 

Bo. 

8172 

400 

o. 

815 

260 

o 

.813 

40O 

0. 

8i35 

470 

o. 

818 

520 

0. 

8148 

510 

0 

818 

285 

O. 

8i55 

530 

o. 

819 

405 

0. 

815 

400 

0 

8167 

700 

0. 

8i55 

700 

0. 

8i75 

370 

0. 

817 

100 

o 

8167 

805 

o. 

8162 

680 

(n)  During   the    night   oil    was   drawn   entirely   through 
and  out  at  the  top  of  five  tubes  which  were  lost. 

(12)  Three  other  tubes  were  set  up  with  these  but  when 
opened  the  oil  in  these  was  81,  81,  and  90  cm.  respectively 
from   the   top,    so   they   were   discarded.     This   unevenness 
between  the  tubes  was  probably  caused  by  using  earth  in 
some  of  them  which  was  not  entirely  cold. 

(13)  Beginning   with    lot    (13)    the   pump    was    run   con- 
tinuously day  and  night. 


i6 


TABL 

(15) 

2  glass,  9  tin. 
Glass,  o,  10. 
Tin,  32,  31,  23, 
23,  24,  26,  9,  16,  14. 

«  II. 

(Continued). 
(16) 

2  glass,  9  tin. 
Glass,  o,  5. 
Tin,  24,  19,  1  6, 

15,  17,  23,  17,  4,  2. 

d7) 

i  glass,  9  tin. 
Glass,  14. 
Tin,  8,  27,  13, 
6,  8,0,  0,0,  o. 

16.75 

16.5 

17 

A 

o 

.800 

300 

0. 

800 

125 

0 

.804 

240 

0 

805 

95 

o. 

8025 

200 

0 

.8055 

120 

0. 

8028 

80 

o 

.8085 

23 

B 

0. 

802 

300 

0. 

8042 

245 

o 

.812 

22O 

0 

808 

90 

0. 

8065 

100 

0 

.812 

155 

0 

8055 

1  20 

0. 

810 

no 

0 

.8127 

45 

C 

o. 

8065 

800 

0. 

8085 

230 

0 

.814 

500 

o 

.810 

350 

0. 

8085 

600 

o 

.8125 

450 

0.8115 

210 

0 

.815 

40 

D 

o. 

8112 

600 

o. 

8117 

435 

0 

.814 

540 

0 

,8142 

525 

0. 

8i35 

650 

0 

.814 

670 

o 

,8122 

680 

o. 

8i37 

370 

0 

.8145 

350 

0 

8155 

200 

0. 

8148 

350 

B 

0. 

8145 

740 

o 

.817 

740 

0 

.820 

400 

see 

0 

.8172 

750 

0 

,818 

4OO 

below 

0 

,817 

820 

B 


D 


TABLE  II.  (Continued). 
08)                                                            (19) 
2  glass,  9  tin            2  glass,  9  tin.                 2  glass,  9  tin.               2  glass,  8  tin 
Glass,  8,  5.             Glass,  14,  17.                     Glass,  o,  o.                    Glass,  o,  9. 
Tin,  17,  2,  15,           Tin,  30,  42,  39,                  Tin,  17,  11,                 5,  Tin,  13,  12, 
19,  12,  22,  21,  o,  o.      28,  35,  33,  42,  30,  42.        18,  12,  15,  13,  18,  11.    23,  15,  19,  ii,  13,  26. 

21 

•5 

23 

O 

.8005 

425 

0 

.806 

200 

0 

.8005 

225 

0.804 

300 

0 

.8015 

190 

o 

.8085 

1  80 

0 

.803 

320 

0 

•8055 

290 

o 

.803 

320 

0 

.8072 

175 

0 

.8042 

200 

0 

.809 

175 

0 

.8055 

75 

o 

.807 

200 

0 

.8078 

475 

0 

.809 

570 

0 

.8078 

680 

0 

.8097 

930 

0 

.808 

500 

0 

•8135 

140 

0 

.8085 

200 

0 

.813 

IOO 

0 

.8095 

170 

0 

.8105 

150 

0. 

8117 

420 

0.8122     500 

0.8128 

560 

0.8128 

475 

O. 

8117 

680 

0.8125     500 

0.813 

725 

0.813 

740 

0. 

813 

660 

0.814       350 

0.815 

400 

0.8185 

1  80 

O. 

8155 

90 

0.817         40 

0. 

8158 

1450 

0 

.816 

930 

0. 

8158 

1000 

0 

.816 

930 

0. 

8165 

420 

0 

.8165 

460 

O. 

8175 

350 

0 

.8185 

400 

0. 

8187 

500 

o 

.8185 

520 

0 

.820 

2OO 

(18)  and  (19)  Two  reservoirs  of  crude  oil  were  used  but  the 
earth  from  all  22  tubes  was  worked  up  together.  Grade  D 
from  all  22  tubes  was  first  united  and  then  for  convenience 
in  working  divided  into  two  portions. 

To  study  further  the  fractionation  on  addition  of  water, 
E  from  lot  1 6  was  collected  in  fourteen  fractions.  The 
weight  of  the  earth  impregnated  with  oil  before  any  water 
had  been  added  was  13.5  pounds,  while  the  weight  of  the 
earth  containing  all  the  water  added,  but  minus  the  oil,  was 
17.5  pounds.  The  earth  was  placed  in  a  galvanized  iron 
garbage  pail  and  the  water  stirred  in  with  an  iron  paddle. 
When  the  first  portion  of  oil  was  liberated  the  mass  was  of 


i8 

the  consistency  of  bran,  but  as  more  water  was  added  it 
turned  to  a  fluid  paste.  When  water  was  added  and  the 
pail  inclined,  oil  would  continue  to  drain  for  half  an  hour  or 
longer  before  the  addition  of  more  water  became  necessary. 
The  oil  which  was  liberated  by  one  lot  of  water,  therefore, 
could  be  collected  in  several  portions,  and  this  was  done  to 
see  whether  the  oil  which  comes  off  immediately  after  the 
addition  of  water  is  the  same  as  that  which  drains  later. 
The  brackets  indicate  that  the  fractions  included  were 
liberated  by  one  addition  of  water. 


0.821 

25 

0.818 
0.818 
0.8193 

70 
70 
250 

0.818 
0.818 
0.818 
0.820 

395 
350 
460 
60 

0.8208 
0.8222 

575 
55 

0.824 
0.828 

170 
16 

0.827 

95 

0.830 

45 

This  occurrence  of  a.  first  fraction  of  higher  specific  gravity 
than  the  ones  immediately  following  occurs  regularly  if  the 
right  amount  of  water  is  added  to  liberate  a  first  fraction  of 
small  enough  volume.  As  the  volume  of  the  fraction  first 
obtained  becomes  larger  it  approaches  nearer  to  the  second 
fraction  in  specific  gravity,  and  will  fall  below  it  if  its  volume 
is  made  too  large. 

The  range  of  specific  gravity  covered  by  this  first  fractiona- 
tion  of  the  crude  petroleum  of  sp.  gr.  0.810  was  from  0.800 
to  0.830.  Oils  of  the  same  specific  gravity  and  of  the  same 
grade  were  united  and  the  products  chilled  and  filtered  to 
remove  all  the  dissolved  paraffine  possible.  The  oils  were 


19 

chilled  and  filtered  out  of  doors  during  the  last  of  December 
when  the  thermometer  stood  at  about  4°  to  8°  C.  Lower 
temperatures  as  well  as  throwing  paraffine  out  of  solution 
would  cause  the  whole  oil  to  thicken.  The  oils  were  filtered 
through  large  plaited  filters  of  drying  paper,  24  hours  or  more 
often  being  required  for  a  filter  to  empty  completely.  The 
lighter  oils  in  grades  A  and  B  deposited  no  paraffine.  The 
heavier  grades  deposited  sometimes  as  much  as  10  per  cent, 
of  their  weight  accompanied  often  by  a  slight  change  in 
specific  gravity. 

When  these  oils  were  filtered  through  earth  again  they 
behaved  as  shown  in  Table  III.  950  cc.  were  used  in  each 
case  and  the  tube  divided  into  five  sections.  A,  as  before, 
is  the  top  8  cm.,  B  the  next  8,  C  the  next  18,  D  the  next  30, 
and  EF  the  rest. 

TABLE  III. — THE  SECOND  FRACTION ATION. 


(20) 

(21) 

(22) 

* 

(23) 

A  0.8015 

A  0.806 

B  0.805 

B  0.8055 

Sp.  gr. 

cc. 

Sp.  gr. 

cc. 

Sp.  gr. 

cc. 

Sp.  gr. 

cc- 

A 

.  o 

.8012 

36 

0 

.8038 

45 

0 

7997 

50 

o  .  8005 

45 

B 

0 

.800 

44 

0 

•8035 

48 

0 

.802 

50 

o  .  8033 

48 

C 

o 

.8012 

68 

O 

•8035 

78 

0 

-8055 

1  08 

0.805 

115 

o 

.8027 

35 

o 

.8052 

28 

D 

0 

.8022 

170 

0 

•805 

1  60 

0 

.8063 

175 

o  .  8063 

1  80 

EF 

o 

.8047 

330 

0 

.807 

320 

o 

.808 

260 

o  .  8085 

260 

683                679                643  648 

(24)               (25)               (26)*  (27)* 

B  0.8065                   B  °-8°9                  B  0.8105  B  0.812 

A        0.8077       38  0.8013       45  0.8075       38  0.8105       42 

B        0.807         50  0.805         50  0.8085       50  0.8105       42 

C         0.808         80  0.807         75  0.8105     100  0.8085       73 

0.810         30  0.810         22 

D        0.8092     160  0.8095     180  0.8125     160  0.8115     140 

EF     0.8115     300  0.8115     350  0.8135     275  0.8145     250 

628                     730                     523  569 


20 


TABUS  III.  (Continued}. 


(28) 

(29) 

(30) 

(30* 

C  0.8095 

C  0.810 

C  0.811 

C  0.811 

A 

0 

.805   52 

0 

.8035 

40 

0, 

8005 

50 

0 

803 

50 

B 

0 

.8065  52 

o 

.808 

40 

o. 

809 

38 

0 

808 

55 

C 

0 

.  8085  70 

0 

.810 

75 

0 

,812 

115 

0 

.813 

105 

0 

.811   28 

o 

.8115 

30 

D 

0 

.811   160 

0 

.8115 

140 

o 

813 

175 

0 

8135 

1  80 

o 

•8135 

40 

BF 

0 

.813  350 

0 

.813 

350 

0 

.8145 

310 

0 

8155 

300 

712 

715 

688 

690 

(32) 

(33) 

(34): 

*         (35)* 

C  0.8115 

C  0.813 

C  0.8135 

C  0.8135 

A 

0 

.806    45 

0 

.8072 

20 

0 

.803 

42 

0 

.8025 

35 

B 

0 

•  807    35 

0 

.811 

35 

0 

,810 

53 

o 

.8077 

35 

C 

0 

.810    60 

o 

.812 

70 

0 

.813 

IOO 

0 

8135 

IOO 

0 

.812    33 

0 

.813 

25 

D 

0 

.812    70 

0 

.8145 

90 

0 

.815 

150 

0 

•  8145 

1  60 

0 

•813    97 

o 

.815 

80 

BF 

0 

.813   103 

0 

.8155 

200 

0 

.817 

300 

o 

.817 

325 

0 

.8135  105 

o 

•  8155 

125 

645 

655 

0 

•813    50 

0 

.818 

35 

0 

•813    47 

680 

Unused,  63 

708 

(36) 

(37)* 

(38)* 

(39)* 

C  0.815 

C  0.8155 

C  0.8155 

€0.8165 

A 

0 

•805    43 

0 

.8053 

50 

0 

,808 

40 

o 

,808 

50 

B 

0 

.8105   40 

0 

.812 

45 

0 

8095 

50 

0 

8145 

50 

C 

0 

.814    98 

0 

.816 

103 

o. 

8i35 

IOO 

0, 

.816 

82 

D 

0 

•815   155 

o 

.8175 

1  60 

0. 

817 

165 

0. 

8i75 

125 

BF 

0 

.817    280 

0 

.819 

310 

0. 

819 

290 

o. 

820 

310 

616 


668 


645 


617 


rrv 


21 


TABLE  III.  (Continued). 


(40)* 

(41) 

(42) 

(43) 

D  0.8135 

D  0.814 

D  0.814 

D  0.814 

A 

0 

.8095 

45 

o 

.8045 

30 

0 

.806 

32 

0 

.806   25 

B 

0 

.8085 

45 

0 

.8115 

45 

0 

.811 

45 

0 

.8097  30 

C 

0 

.811 

95 

o 

.8135 

75 

0 

.813 

92 

0 

.814   -50 

0 

.8165 

28 

D 

0 

.8155 

165 

o 

.818 

140 

0 

.8175 

140 

0 

.8157  145 

BF 

0 

.817 

320 

0 

.821 

300 

o 

.8195 

310 

0 

.8175  400 

670 

618 

619 

650 

(44) 

(45) 

(46) 

(47) 

D  0.814 

D  0.814 

D  0.8145 

D  0.815 

A 

0 

.8008 

45 

0 

.800 

50 

0 

.808 

45 

0 

.800    42 

B 

0 

.8077 

50 

0 

.8065 

55 

o 

.8115 

40 

0 

•807    47 

C 

0 

.814 

103 

0 

.8125 

100 

0 

•8135 

65 

0 

.814   no 

0 

.8155 

30 

D 

o 

.8175 

1  60 

0 

.816 

160 

0 

.817 

105 

0 

.816   150 

0 

.818 

58 

EF 

0 

.819 

310 

0 

.817 

300 

0 

.8195 

1  80 

0 

•819   330 

668 

665 

0 

.8202 

120 

679 

0 

.821 

53 

' 

696 

(48) 

(49) 

(50) 

(SO 

D  0.815 

D  0.8155 

D  0.8155 

D  0.8155 

A 

0 

.810 

37 

0 

.8045 

40 

0 

.8105 

45 

0 

.  8058   40 

B 

0 

.805 

47 

0 

.8n 

48 

0 

.8148 

47 

0 

.810    40 

C 

0.812 

105 

o 

.815 

98 

0 

.810 

IOO 

0 

.8132   60 

0 

.8145   50 

D 

0 

.817 

1  60 

0 

.8185 

160 

0 

.815 

140 

0 

•8172   75 

o 

.8188   55 

o 

.8188   38 

EF 

0 

.819 

300 

0 

.820 

310 

0 

.819 

400 

0 

.820    38 

649 

656 

732 

0 

.819   loo 

, 

0.8208   30 

0 

.8208   45 

0 

.  8208   30 

0 

.8208   95 

Unused,  40 

736 


22 

III.    (Continued). 


(52) 

(53)* 

(54) 

(55) 

D  0.816 

D  0.816 

D  0.8165 

D  0.8165 

A 

0 

.806   38 

o 

.803 

43 

o 

.806 

47 

o  .  8095 

42 

B 

0 

.8115   42 

0 

.8105 

30 

0 

.811 

48 

o 

.8135 

40 

C 

o 

.814    70 

o 

.815 

IOO 

0 

•815 

98 

o 

.8145 

77 

0 

•8175  25 

D 

0 

.8185  125 

o 

.8185 

175 

0 

.8188 

150 

o 

.8188 

150 

BF 

0 

.821   300 

0 

.820 

290 

0 

.8208 

300 

0 

.821 

295 

700 

638 

643 

604 

,  ,.  » 

(56)* 

(57)* 

(58)* 

(59) 

D  0.8165 

D  0.817 

D  0.818 

D  0.8187 

A 

0 

.806    45 

0 

8075 

40 

0 

,808 

45 

0 

.8ll 

40 

B 

o 

.810    45 

o 

.8115 

40 

o 

.8135 

45 

0 

.812 

45 

C 

0 

•8145   95 

0 

815 

IOO 

0 

.817 

105 

o 

.814 

92 

D 

0 

.8185  160 

o 

.818 

130 

0 

,820 

150 

0 

.819 

150 

BF 

o 

.821   295 

0 

.821 

330 

0 

.822 

300 

0 

.823 

305 

640 

640 

645 

632 

(60)* 

(61) 

(62) 

* 

(63) 

* 

D  0.8205 

B  0.814 

E  0.8163 

E  0.817 

A 

0 

•8045   45 

0 

.8075 

33 

o 

•8i55 

42 

o 

.804 

45 

B 

o 

•813    45 

o. 

810 

35 

o. 

808 

50 

o. 

8075 

50 

C 

0 

•8i75   90 

o 

.8125 

80 

0 

8095 

70 

0 

8145 

102 

0 

.812 

25 

D 

o 

.822   170 

0 

.818 

125 

0 

-8i75 

105 

o 

.8205 

150 

o 

.8182 

32 

BF 

0 

.823   270 

o 

.8245 

300 

0 

•823 

250 

0 

•8245 

300 

Unused,  70 



0 

•8255 

4i 



573 



647 

692  615 


23 

III.  (Continued). 


(64)* 

(65)* 

(66)* 

(67) 

E  0.817 

E  0.818 

E  0.818 

E  0.818 

A 

0. 

805   42 

0. 

8065 

90 

O. 

805 

38 

0, 

805 

40 

0. 

809 

20 

B 

0. 

810    42 

0. 

810 

110 

0. 

811 

38 

0 

811 

45 

C 

0. 

8i45   75 

o. 

8i55 

186 

0. 

8135 

104 

o 

8145 

85 

0. 

817 

50 

D 

o, 

820   135 

0. 

8205 

385 

o. 

819 

175 

0 

8185 

125 

0. 

8205 

75 

EF 

0. 

8255  235 

o. 

8255 

650 

0. 

8235 

240 

o 

824 

325 

-  — 

0. 

8255 

260 





529 



695 

620 

1826 

3 

tubes. 

(68)* 

(69) 

(70) 

(71) 

* 

E  0.8185 

E  0.819 

E  0.819 

E  0.819 

A 

0. 

8205   15 

o. 

804 

24 

0. 

8115 

21 

o 

8095 

23 

B 

o. 

8043   35 

0. 

808 

40 

0. 

814 

31 

0 

8085 

34 

C 

0. 

810    60 

o. 

8i45 

85 

0. 

815 

90 

0 

,814 

80 

0. 

812    30 

D 

0. 

817   160 

0. 

8i95 

140 

0. 

8165 

I2O 

o 

.820 

1  60 

EF 

o, 

8225  300 

0. 

824 

300 

0, 

824 

330 

0 

.824 

280 

590 

589 

592 

577 

(72)* 

(73)* 

(74) 

(75) 

E  0.8195 

Eo. 

8195 

E  0.8195 

E  0.8197 

A 

0. 

8i45   30 

0. 

8055 

34 

0, 

,816 

40 

0 

.8025 

40 

B 

o 

8105   42 

o. 

811 

45 

0 

8i35 

42 

o 

8105 

38 

C 

o, 

8135  103 

0, 

8i55 

80 

o 

809 

65 

o 

.816 

90 

o 

814 

34 

D 

0, 

8195  160 

0. 

820 

120 

0 

8185 

160 

0 

.822 

150 

BF 

0, 

824  285 

0. 

824 

290 

o 

,824 

260 

0 

•8255 

300 





0 

,827 

30 



620  569  618 

631 


TABLE  III.   (Continued). 


(76)*- 

(77)* 

(78) 

(79)* 

E  0.820 

E  0.8205 

E  0.8215 

E  0.822 

A 

0. 

8045 

48 

0 

.806 

32 

0. 

8045 

28 

0 

.8105   32 

B 

0.812 

40 

0 

.8125 

45 

o. 

8135 

36 

0 

.8145   42 

C 

o. 

817 

91 

0 

.8175 

90 

o. 

8185 

78 

0 

.819    77 

D 

0. 

822 

155 

0 

.823 

100 

o. 

823 

150 

0 

•8225  155 

EF 

o. 

826 

260 

0 

.8245 

330 

o. 

8275 

300 

0 

.827   280 

594 

597 

592 

586 

t 

(80) 

(81) 

(82) 

(83)* 

Eo. 

822 

Eo 

.822 

E  0.824 

A-B  0.804 

A 

o. 

817 

30 

0 

.8083 

26 

o. 

8125 

48 

o 

.803    32 

B 

0. 

810 

40 

0 

.814 

40 

0. 

8127 

48 

0 

•8035   25 

C 

0. 

8i53 

46 

0 

•  8185 

92 

o. 

818 

53 

0 

•8035   63 

0. 

8163 

42 

0. 

819 

50 

D 

0. 

8225 

1  60 

0 

.824 

140 

0. 

8245 

175 

0 

.  804   140 

EF 

0. 

8265 

295 

o 

.8265 

270 

0. 

828 

200 

0 

.806   275 

o. 

830 

90 



613 

568 

left 

,50 

535 

7H 

(84) 

* 

(85)* 

(86)* 

(87)* 

A-B  0.8065 

A-B  0.808 

B-C-D  0.8125 

B-C-D  0.8125 

A 

0. 

8035 

40 

0 

.8085 

30 

0. 

805 

32 

o 

.  805    80 

B 

o. 

8055 

40 

0 

.807 

30 

o. 

808 

42 

0 

•8085   73 

C 

o. 

809 

80 

0 

.8065 

92 

o. 

813 

85 

0 

.812   118 

0 

•813    75 

D 

0. 

8085 

155 

0 

.8085 

"5 

o. 

815 

175 

o 

.815   285 

EF 

0. 

8n 

300 

0 

.8115 

330 

o. 

820 

280 

0 

.8175  520 

615 

597 

614 

H5I 

2 

tubes. 

J 


A 
B 
C 
D 

BF 


25 
III.  (Continued). 


(88)* 

(89) 

* 

(90) 

* 

(91)* 

C-D-E  o. 

813 

C-D-E  o. 

813 

B-C-D  0.8145 

D-Eo. 

815 

0 

8035 

40 

o 

8035 

130 

o 

.8065 

130 

0. 

801 

165 

0 

,807 

20 

0 

.808 

27 

0.8025 

176 

o 

808 

40 

0 

8077 

1  60 

0 

.809 

137 

o. 

8075 

206 

0 

.8115 

20 

o. 

8085 

156 

0 

8115 

73 

o 

8125 

330 

o 

.813 

305 

0. 

812 

330 

0 

813 

30 

0, 

813 

60 

0 

.815 

40 

0. 

812 

512 

0. 

8155 

160 

0 

815 

550 

o 

.815 

560 

0. 

817 

340 

o 

8175 

90 

0 

.8175 

75 

o. 

8i7 

800 

0. 

8i7 

150 

633 


-"•"•/O    '-'O'-'    '•"*•!  3    113 

.818   425  0.818   410 


0.8215  etc. 


2595 
4  tubes.     4  tubes. 


2479 


5568 


9  tubes. 


(92)* 

(93) 

(94) 

D-E  0.8163 

F  0.822 

Fo.822 

A 

0. 

805 

84 

0. 

8107 

35 

0. 

804 

28 

o. 

8075 

20 

B 

0. 

807 

100 

0. 

810 

43 

0. 

808 

37 

0. 

8115 

20 

C 

o. 

815 

205 

o. 

814 

70 

0. 

8165 

63 

0. 

816 

45 

o. 

816 

25 

o. 

817 

30 

D 

0. 

820 

350 

0. 

8215 

156 

0. 

8218 

146 

0. 

820 

102 

BF 

0. 

8225 

500 

0. 

8285 

250 

o. 

831 

255 

0. 

8225 

480 

0. 

831 

60 



1906 


639 


559 


3  tubes. 

*  950  cc.  were  needed  for  each  tube  and  for  many  tubes  this  amount 
was  available  of  the  same  grade  (A,  B,  C,  etc.),  and  of  the  same  specific 
gravity.  In  some  cases,  though,  it  was  necessary  to  unite  oils  of  the 
same  grade  which  differed  slightly  in  specific  gravity.  Such  samples 
differed  in  no  case  by  more  than  0.0015  and  are  all  marked.* 

To  chill  and  filter  these  products  of  two  fractionations 
would  have  entailed  too  much  loss.  As  it  was,  much  uniting 
of  samples  which  differed  but  silghtly  from  one  another  was 
necessary  to  obtain  sufficient  oil  for  further  fractionation. 
The  unions  which  were  made  are  given  in  Table  IV. 


26 


5 
D 

-* 

H 

s 

5 

H 

j 

0 

04 

to 

1 

6 

p 

5 

to 

M 
M 

00 

6 
pq 

CO 

to 

M 

00 

6 
o 

j 

3 

3 

to 

04 

O   to 

^  ON 

to  O 
t-^oo 

04  VO 
ON  04 

00 

HH 

eg 

o_ 

00            O 
O            04 

v§ 

H 

M 

04    M 

M 

* 

CO        00 

s 

to 

CO 

to  co 

to 

to 

to       to 

O4 

a 

<? 

o"  o* 

VO  vO 
0   0 

? 

o* 

M 

M            O4 

CO 
M 

c 

OO 

oo  oo 

00  00 

00  OO 

00 

oo 

00 

oo       oo 

00 

H 

4 

6 

6  6 

6  6 

6  6 

6 

6 

6 

6      6 

6 

=4 

PQ 

PPQ 

WP 

0«1 

^ 

« 

^ 

» 

O 

5 

Lf 

H 

3 

1 

CO 

to  O 

CO  0 

1^00 

s 

1 

o 

04 

MOO 
ON^ 

ON  t^» 

0 
ON 

0 

5 

to 

to 

to 

to 

to  «o  »o 

to  to 

to 

a 

y*^ 

•*t-  to 

o  o 

t~>.oo 

^ 

r^ 

-*N 

CO  CO  CO 

H 
•£ 

<g 

00  00 

oo  oo 

oo  oo 

s 

(g 

00 

00  00  00 

OO  00  00 

oo 

O 

o  o 

O   0 

o  o 

0 

0 

6 

666 

6  6  6 

6 

3 

H 

X 

H 

i 

< 

« 

<3  PQ 

00 

0 

<d 

0 

<1WP 

1 

PQOW  g 
en 

o  !_  5 

t 

H 

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D 

00 

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CO  O 
vO    «O 

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M   rf  Th 

tovo 

04 

O  00 
04     CO 

£ 

J°  8  S 

s 

00  "8    R  ^ 

0    ^ 

£ 

M 

M            O4 

M      CO   tO 

.!=? 

M  M  cog> 

10  J*. 

t4 

co 

to  to 

OO    to 

04    !>• 

to 

CO 

."tn 

10  to  to*d 

."ti  "     " 

3 

CO 

00 

to  tovo 

OOO 

0*0 

ON 

t>.  !>. 

/-\         /-\ 

s 

^  § 

0 

oo 

ao  oo 

00  00  00 

w     w 
00  00 

OO 

eg  eg 

00 

oo  oo  oo 

o 

oo  oo  oo  Q 

°°  o. 

j 

o 

O    0 

OOO 

0   0 

0 

0    0 

Q 

OOO 

6    6    6  £H 

9 

5 

f-y^ 

f^yj 

2 

pq 

o< 

<J« 

<JPQ 

< 

« 

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owo 

o 

PQ  W  PO 

P  P  PtfP 

H 

> 
H 

*    £ 

fr 

to 

0 

to 

00 

/-\ 

2 

to  to 

M     04 

ro 

to 

CO         ^  ^ 

to       to'co 

r^-   IO   tOvO 

a 

*>   eg 

00 

U 

00 

1 

00 

00  00 

00 

oo       oo  oo 

oo  oo  oo  oo 

4 

q 

£  6 

6 

6 

o 

6 

6  6 

o 

6      66 

6666 

-t 

-8    to 

M-       ON 

i 

t^ 

ON 

00 

ON 

ON 
ON 

85 

01 

0 

CO               Tf    tO 

0          00 

vO    t^OO    ON 

0000 

1 


oo 
0 


«o 


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ooooooooooooooooooooooooooooco 

606666660000000 


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ON  O    M    CM    CO 


28 

950  cc.  of  each  of  these  were  fractionated  by   earth  again, 
with  the  results  as  given  in  Table  V. 


TABLE  V. — THK  THIRD  FR ACTION ATION. 


(95) 

(96) 

(97) 

(98) 

A-Do 

.805 

A-EF  0.807 

A-C  0.8085 

A-D  0.8085 

A 

0 

.8065 

33 

0. 

8045 

37 

o. 

806 

40 

0 

.  8047  38 

B 

0 

.805 

33 

0, 

806 

38 

0. 

8068 

40 

O 

.8052  38 

C 

0 

.804 

62 

o 

8065 

65 

0. 

807 

58 

0 

.  808   70 

0 

.805 

40 

0 

.8083 

25 

0. 

8095 

18 

0 

.  8093  30 

D 

0 

.8055 

150 

0 

,808 

142 

o. 

8093 

154 

0 

.8095  132 

EF 

o 

.808 

315 

o 

8095 

250 

0. 

812 

295 

0 

•811   335 

633 

557 

-605 

643 

(99) 

(100) 

(101) 

(102) 

A-Co. 

8105 

EF  0.8115 

C-EFo.8i25 

C  0.813 

A 

0 

.8105 

33 

0 

.8065 

30 

0. 

808 

33 

o 

.  806   26 

B 

0 

.810 

36 

o 

.809 

36 

0 

8085 

34 

0 

•8105   33 

C 

0 

.8075 

7i 

0 

.810 

60 

0 

811 

54 

0 

.8105   50 

0 

.8085 

17 

0 

.812 

20 

o 

8145 

22 

o 

.813    17 

D 

o 

.811 

H5 

o 

.812 

136 

0 

8145 

162 

o 

.813   136 

EF 

0 

.814 

300 

0 

.815 

315 

0 

.817 

295 

0 

•8i57  365 

572 

597 

600 

627 

(103) 

(104) 

(105) 

(106) 

B-Co. 

8135 

D-EF  0.814 

C  0.814 

C-D  0.8145 

A 

0 

.8065 

28 

0 

.8042 

35 

o 

.804 

40 

o 

•803    33 

B 

0 

.810 

33 

o 

.8115 

36 

0 

.810 

40 

0 

.810    40 

C 

0 

•8135 

60 

0 

.8125 

60 

0 

.8142 

58 

o 

•8i45   54 

0 

.8165 

18 

0 

.8147 

28 

o 

.816 

25 

o 

.8l6     22 

D 

o 

•815 

150 

0 

.815 

175 

0 

.8163 

270 

o 

.8l6    150 

EF 

0 

.817 

325 

o 

.819 

230 

0 

•  8185 

280 

0 

.8185   260 

614  564  713  559 


29 
TABLE  V.   (Continued). 


(107) 

(108) 

(109) 

(no) 

D  0.815 

EF  0.8155 

D  0.8163 

D  0.817 

A 

0 

•  8035 

45 

0 

.809 

52 

0 

•810    33 

O 

.8065 

35 

B 

0 

.8115 

47 

o 

.811 

47 

0 

.8105   45 

O 

.8125 

40 

C 

0 

.815 

85 

o 

.815 

55 

o 

•8132   55 

0 

.817 

68 

0 

.8177 

30 

0 

.815 

40 

0 

•8i45   33 

0 

.818 

30 

D 

0 

.8175 

156 

0 

.8165 

170 

0 

.8185  140 

0 

•  8195 

H5 

EF 

o 

.8195 

300 

0 

.8185 

255 

0 

.8215  275 

o 

.821 

290 

663 

619 

58i 

608 

(ill) 

(112) 

(113) 

(114) 

EF  0.817 

C-D  0.8175 

EF  0.8175 

EF  0.8187 

A 

0 

.8043 

30 

0 

•  8145 

35 

0 

•8065   35 

0 

.817 

30 

B 

0 

.8105 

32 

0 

.811 

32 

0 

.812    48 

0 

.8065 

25 

C 

0 

.8152 

65 

o 

.8165 

60 

0 

•8i55   75 

0 

.8122 

30 

0 

.816 

43 

0.818 

30 

0 

•8175   18 

0 

.813 

15 

D 

0 

.8182 

160 

o 

.819 

150 

0 

.8185  150 

0 

.8175 

150 

EF 

0 

.8205 

290 

0 

.822 

245 

0 

.8225  283 

0 

.822 

340 

620 

552 

609 

590 

(115) 

(116) 

(117) 

(118) 

D  0.819 

EF  0.819 

D  0.819 

EF  0.819 

A 

0 

•8055 

16 

0 

.8032 

30 

0 

•8045   33 

0 

.805 

30 

B 

0 

.807 

lost 

0 

.8115 

36 

0 

-813    38 

0 

.813 

30 

C 

0 

.816 

43 

0 

.816 

52 

0 

.8175   60 

0 

.8165 

60 

0 

.817 

30 

0 

.820 

21 

0 

•8i75   34 

10 

D 

0 

.820 

130 

0 

.8205 

1  60 

0 

.8215  150 

0 

.821 

154 

EF 

0 

.8235 

300 

0 

•8235 

240 

0 

•8235  325 

0 

•8243 

295 

lost 

539 

640 

579 

(119) 

(120) 

(121) 

(122) 

EF  0.8195 

D  0.820 

EFo.82i 

EF  0.82  15 

A 

0 

.805 

23 

0 

.805 

33 

o 

•8075   33 

o 

.803 

4i 

B 

0 

.814 

35 

0 

.811 

35 

0 

.814    41 

0 

.811 

43 

C 

o 

.8165 

58 

0 

.817 

53 

0 

.8182   63 

0 

.8165 

60 

0 

.8175 

32 

0 

•8175 

35 

0 

.81,9    18 

0 

.8l8 

23 

D 

0 

.8205 

152 

0 

.822 

165 

0 

.822   150 

0 

.8225 

182 

EF 

0 

.823 

300 

0 

-825 

310 

0 

•8245  273 

0 

.828 

270 

600 

633 

578 

629 

(123) 

30 

TABLE  V.  (Continued). 
(124)                     (125) 

(126) 

D-EF  0.822 

EF  0.8225 

EF  0.8235 

D-EF  o. 

824 

A 

0 

.808 

34 

0.807 

31 

0.804 

35 

0.805 

35 

B 

0 

.813 

35 

o  .  8095 

27 

0.813 

40 

0.814 

35 

C 

0 

.8178 

52 

0.8175 

65 

0.8185 

70 

0.820 

60 

0 

.8192 

42 

0.8185 

17 

0.8195 

21 

0.821 

20 

D 

0 

.8233 

155 

0.8232 

150 

0.8252 

144 

0.8253 

170 

EF 

o 

.8265 

260 

0.8275 

300 

0.829 

280 

0.828 

300 

578 

590 

590 

62O 

(127) 

'   ,_- 

EF  0.8255 

A 

0 

.8055 

45 

B 

o 

.8155 

40 

C 

0 

.821 

75 

0 

.823 

25 

D 

o 

.8275 

170 

EF 

0 

.830 

280 

635 

From  the  products  of  the  third  fractionation,  oil  in  sufficient 
quantity  and  of  five  grades  was  obtained  by  uniting  frac- 
tions as  given  in  Table  VI.,  the  results  of  the  fourth  fractiona- 
tion being  given  in  Table  VII. 


10  CM  co  co  10  O  »o 
M  vo  <N  1000  -3-vo 

COM 


.. 

Ho 


10 


&OOOOOOOOOOQOOOO 
fjj  p.    ....... 

aooooooo 

5° 

s 

p 


o  o  o 

t^  10  t^ 


CO 


»O 

vO 


00  00  00 

odd 

ppp 


10  o   O 

VO  IO  rf 


VO  >O  IO 

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33 
TABLE  VII. — THE  FOURTH  FRACTIONATION. 


(128) 

(129) 

(130) 

(131) 

C-EF 

0.815 

D-EF  0.8  168 

D-EF  0.819 

D-EF  0.8205 

A 

o 

•8135 

19 

0.812 

30 

0.8115 

24 

0.8095 

18 

B 

0 

.815 

27 

0.8122 

42 

0.8127 

35 

0.813 

26 

C 

0 

.8118 

50 

0.8165 

55 

0-8173 

60 

0.819 

45 

0 

-813 

15 

0.818 

25 

0.8185 

22 

0.8195 

17 

D 

o 

.8147 

140 

0.818 

1  60 

0.820 

160 

0.8215 

130 

BF 

o 

•8i75 

360 

0.8195 

305 

0.8215 

310 

0.824 

340 

611 

617 

611 

576 

(132) 

D-EF 

0.823 

A 

o 

.8092 

35 

B 

lost 

35 

C 

0 

•8195 

60 

0 

.8213 

25 

D 

0 

•8235 

150 

BF 

0 

.826 

280 

585 

To  better  compare  the  oils  of  different  specific  gravities 
which  were  obtained  by  the  process  just  described  five 
samples  of  300  cc.  each  were  separated  by  distillation  into 
ten  fractions.  Bach  was  distilled  in  the  same  500  cc.  distil- 
ling bulb  which  was  heated  by  an  electric  stove  which  en- 
tirely surrounded  the  bulb.  Bach  was  first  heated  to  200° 
under  atmospheric  pressure  and  then  to  360°  under  50  mm. 
pressure.  The  diminished  pressure  was  obtained  with  a  large 
Chapman  water  pump  and  kept  constant  at  50  mm.  by  the 
use  of  a  valve  which  automatically  admitted  air  to  the 
evacuated  system  whenever  the  pressure  fell  below  50  mm. 

This  valve  was  constructed  from  a  piece  of  iron  pipe  one 
inch  in  diameter  and  five  feet  long.  The  lower  end  was 
closed  with  a  cap  and  the  pipe  filled  with  mercury  to  a  depth 
of  76  cm.  The  upper  end  of  the  pipe  was  closed  with  a  two- 
hole  rubber  stopper.  In  one  hole  was  a  long  glass  tube 
with  the  lower  end  beveled,  which  reached  to  the  bottom 
of  the  mercury  and  which  could  be  raised  or  lowered  as  the 


34 

barometer  varied  from  day  to  day.  In  the  other  hole  of  the 
stopper  was  a  tube  which  passed  just  through  the  stopper 
and  which  was  connected  on  the  outside  with  the  apparatus 
to  be  exhausted.  To  prevent  mercury  from  being  drawn 
up  and  over  into  the  apparatus  by  the  air  admitted,  the  end 
of  the  tube  inside  the  stopper  was  drawn  out  and  bent  at  a 
right  angle  and  over  this  was  slipped  a  cap  made  of  larger 
tubing  which  was  closed  at  the  bottom  but  which  had  a  fine 
opening  in  the  side  for  air.  This  cap  was  about  six  cm.  long 
and  extended  about  three  cm.  below  the  end  of  the  tube 
inside.  If  any  mercury  passed  through  this  first  fine  opening 
into  the  cap,  it  would  fall  to  the  bottom  without  being  drawn 
over  into  the  apparatus  or  clogging  the  fine  opening  in  the 
tube  leading  thereto.  With  this  valve  there  was  no  diffi- 
culty in  keeping  a  pressure  of  50  mm.  constant  to  within 
one  mm. 

Bach  distillate  of  sufficient  volume,  which  was  not  tpo 
viscous  or  partly  solid,  was  tested  as  to  specific  gravity, 
viscosity,  and  per  cent,  absorbed  when  treated  with  con- 
centrated sulphuric"  acid  (sp.  gr.  1.84). 

Viscosity  was  measured  by  taking  the  time  of  flow  of  a 
measured  volume  of  oil  through  a  capillary,  the  viscometer 
used  being  the  one  described  by  Ostwald  and  Luther  as 
modified  by  Jones  and  Veazey.1  The  capacity  of  the  small 
bulb  was  4.5  cc.  and  the  diameter  of  the  capillary  such  as  to 
require  for  from  five  to  eight  minutes  for  that  amount  of  oil 
to  flow  through  it,  and  one  minute  2.6  seconds  for  the  same 
amount  of  water.  The  viscosity  as  well  as  specific  gravity 
was  always  measured  at  20°. 

Viscosities  have  been  calculated  from  the  following  formula : 

TS 
V  =  *7o   ATA        in   which   rj0  is  the  coefficient   of   viscosity   for 

io'wo 

water,  S0  is  the  sp.  gr.  of  water,  and  T0  the  time  of  flow  of 
water  through  any  given  capillary  at  a  given  temperature ;  rj 
is  the  viscosity  coefficient  of  the  solution  investigated,  S  is  its 
specific  gravity  as  compared  with  water  as  unity  at  any  given 
temperature,  and  T  is  the  time  of  flow  of  the  given  solution 
1  Z.  physik.  Chem.,  61,  651. 


35 

at  that  temperature.     The  value  for  pure  water  at  20°  was 
taken  from  the  work  of  Thorpe  and  Rodger.1 

Thirty  cc.  of  each  of  these  distillates,  where  that  much  oil 
was  available,  all  the  oil  there  was  where  the  volume  was 
less  than  30  cc.,  were  mixed  with  an  equal  volume  of  con- 
centrated sulphuric  acid  (sp.  gr.  1.84)  and  shaken  half  an 
hour  or  longer  in  a  shaking  machine.  The  oil  and  acid  were 
then  poured  into  a  separating  funnel  and  the  acid  drawn  off. 
The  oil  was  then  washed  twice  with  water,  once  with  aqueous 
NaOH,  again  with  water,  and  then  with  this  last  wash  water 
poured  into  a  burette  and  allowed  to  settle.  After  standing 
over  night  the  volume  was  read.  -  , 

The  oils  boiling  below  200°  (50  mm.)  separated  clear,  but 
the  heavy  distillates  were  milky  from  water.  The  volume  of 
these  milky  oils  was  read,  their  specific  gravity  taken,  and 
then  the  milkiness  was  removed  by  shaking  and  heating  to 
60°  or  so  with  CaCl2.  The  specific  gravity  of  the  clear  oil 
was  then  taken  and  the  proper  correction  made  to  the  milky 
volume.  In  no  case,  however,  was  this  correction  at  all 
large,  and  only  for  the  three  or  four  heaviest  oils  did  it  ex- 
ceed one-half  of  i  per  cent.,  the  largest  correction  of  all  being 
2.6  per  cent,  for  the  distillate  between  23o°-26o°  of  the  oil 
of  sp.  gr.  0.824.  An  attempt  to  treat  with  acid  the- oils 
selected  to  be  distilled,  resulted  in  so  much  loss  from  the 
formation  of  emulsions  that  the  loss  in  volume  and  change 
in  specific  gravity  could  not  be  determined  with  any  degree 
of  accuracy. 

1  Phil.  Trans.,  i8sA,  397  (1894). 


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"Fluid"  means  that  the  oil  at  20°  was  partly  solid  but 
would  flow  when  the  bottle  was  inclined;  "solid,"  that  the 
bottle  could  be  turned  upside  down  without  the  oil  changing 
shape. 

It  was  hoped  that  sulphuric  acid  of  the  strength  used 
(sp.  gr.  1.84)  would  dissolve  only  unsaturated  hydrocarbons 
and  leave  untouched  the  paraffines  and  benzene.  By  long- 
continued  shaking  at  ordinary  temperature,  however,  with 
acid  of  this  strength,  benzene  is  dissolved,  provided  that  the 
acid  is  in  large  excess.  One  hundred  cc.  of  benzene  were 
completely  dissolved  in  434  cc.  of  acid  on  being  shaken  four 
hours. 

Three  of  the  distillates  which  had  been  shaken  with  acid, 
however,  gave  no  action  when  treated  with  a  mixture  of  equal 
parts  concentrated  sulphuric  acid  and  fuming  nitric  acid, 
while  distillates  which  had  not  been  previously  shaken  with 
sulphuric  acid  were  acted  upon  by  this  nitrating  mixture. 
The  action  of  the  sulphuric  acid,  therefore,  appears  to  have 
been  complete. 

The  action  of  sulphuric  acid  shows  that  over  90  per  cent,  of 
the  oil  dealt  with  consists  of  paraffine  hydrocarbons,  and 
that  in  the  filtration  through  earth  the  paraffine  hydro- 
carbons tend  to  collect  at  the  top  of  the  tube  and  the  un- 
saturated hydrocarbons  at  the  bottom. 

The  increasing  amount  dissolved  by  sulphuric  acid  in  the 
heavier  oils  may  be  seen  in  the  following  curves:  The 
abscissas  represent  temperatures  and  the  ordinates  volumes. 
The  same  distance  upon  the  X  axis  is  taken  to  represent  a 
distillate,  whatever  be  the  number  of  degrees  over  which  it 
may  have  been  collected.  The  upper  curve  represents  the 
per  cent,  of  the  total  volume  which  distilled  between  given 
temperatures;  the  lower  curve,  the  per  cent,  of  the  total 
volume  recovered  which  was  not  absorbed  by  sulphuric  acid 
(i.  e.,  the  paraffine  hydrocarbons).  For  the  upper  curve  the 
ordinates  were  obtained  by  dividing  the  number  of  cubic 
centimeters  in  the  distillate  by  the  total  volume  of  oil  re- 
covered. For  the  lower  curve  the  ordinates  were  obtained 
by  dividing  the  number  of  cubic  centimeters  in  the  distillate 


Temp.         o°  150°         200°         140°         200°  230°       260° 

Normal  pressure.  50  mm.  pressure. 


Temp.         o°         150°         200° 


Normal  pressure. 


mm.  pressure. 


Temp.        o°         150°         200°         140°         200°         230°         260° 


Normal  pressure. 


50  mm.  pressure. 


43 

not  absorbed  by  sulphuric  acid,  by  the  total  volume  of  oil 
recovered. 

The  area  between  the  two  curves  represents  the  proportion 
of  hydrocarbons  soluble  in  sulphuric  acid,  which  it  will  be 
seen  is  greatest  for  the  oils  of  highest  specific  gravity. 

On  referring  to  Tables  III.  and  V.  it  will  be  noticed  that 
there  are  several  tubes  given  where  the  specific  gravity  of 
the  oil  of  grade  A  is  heavier  than  grade  B  and  sometimes 
than  grade  C.  Tubes  where  this  irregularity  is  marked  are 
4$,  62,  68,  72,  74,  and  80  of  Table  III.,  and  112  and  114  of 
Table  V.  A  slight  irregularity  appears  in  20,  21,  24,  27, 
40,  71,  and  85  of  Table  III.  and  in  99  of  Table  V.  If  the 
oils  in  these  cases  are  not  colorless,  the  color  is  strongest 
where  the  specific  gravity  is  greatest,  so  that  although  oil 
of  the  grade  A  has  passed  through  the  most  earth  it  is  yet 
more  strongly  colored  than  oil  of  grade  B  or  C. 

No  reason  for  this  variation  has  been  established.  It 
should  be  remembered,  however,  that  the  different  oils  rise 
in  the  earth  with  differing  velocities,  not  because  they  differ 
from  one  another  in  specific  gravity  but  because  they  differ 
in  surface  tension.  A  rough  attempt  was  made  to  measure 
relative  surface  tensions  by  measuring  the  height  to  which 
different  oils  rise  in  the  same  capillary  tube,  but  although 
a  kathotometer  was  used  and  the  level  of  the  oil  in  the  capillary 
brought  to  the  same  spot  each  time,  the  work  sufficed  only 
to  show  that  the  difference  between  the  surface  tension  of  the 
oils  obtained  was  so  slight  as  to  require  very  careful  measure- 
ment for  the  results  to  be  of  any  value. 

That  viscosity  shows  the  same  irregularity  in  these  oils 
as  color  and  specific  gravity,  appears  from  the  following 

measurements. 

(62)  (68) 

Sp.  gr.  Vis.  Sp.  gr.  Vis. 

A 0.8155  0-0539  0.8205  0.0626 

B 0.808  0.0469  0.8043  0.0469 

C 0.8095  0.0509  0.810  0.0520 

0.812  0.0555  0.812  0.0554 

D 0.8175  0.0525  0.817  0.0524 

0.8182  0.0535 

BF 0.823  0.0612  0.8225  0.0606 


44 

In  (50)  of  Table  III.  an  irregularity  appears  in  grade  B 
which  is  also  found  in  the  viscosity. 

(5o) 

Sp.  gr.  Vis. 

A 0.8105  0.0532 

B 0.8148  0.0559 

C 0.810  0.0526 

D 0.815  0.0526 

EF '.....     0.819  0.0552 


The  oils  obtained  by  one  fractionation 
leum  have  the  following  viscosities,  the 
being  those  previously  given  in  Table  I. 


of  the  crude  petro- 
fractions  measured 


(I) 

(2) 

(3) 

Sp.  gr. 

Vis. 

Sp.  gr. 

Vis. 

Sp.  gr. 

Vis. 

A 

0. 

796 

o 

0376 

0.8012 

0 

.0408 

0. 

8022 

0 

.0401 

B 

0 

808 

0 

0529 

0.804 

0 

•0485 

0 

803 

0 

.0470 

C 

o 

8125 

0 

0501 

0.807 

0 

•0443 

0 

8075 

o 

•0453 

o 

8137 

0 

.0529 

0.809 

0 

.0476 

0 

810 

0 

.0471 

D 

0 

815 

0 

.0504 

0.8125 

0 

.0460 

0 

,812 

0 

.0472 

E 

o 

,818 

0 

0521 

0.8l85 

0 

•0537 

O 

8175 

0 

.0529 

F 

o 

,8205 

.  . 

0.823 

.  . 

o 

.821 

That  the  viscosity  does  not  increase  with  the  specific 
gravity,  particularly  with  the  higher  fractions,  is  apparent 
in  two  of  the  three  series  just  given.  The  same  is  also  shown 
in  the  following  four  tubes  taken  from  Table  III. 


A 
B 

C 

D 
EF 

(21) 

Sp.  gr. 

0.8038     o 
0.8035     o 
0.8035     o 
0.8052     o 
o  .  805       o 
0.807       o 

Vis. 
0465 
0456 
0456 
0485 

0479 
.0480 

(22) 

Sp.  gr. 

0.7997 

0.802 

0.8055 

0.8063 
0.808 


Vis. 

o . 042 i 

0.0485 
0.0502 

o . 0496 

0.0510 


(47) 


A 
B 
C 
D 
EF 


Sp.  gr. 
O.SOO 
0.807 
0.814 

0.816 
0.819 


Vis. 

0.0453 
0.0538 
0.0542 
0.0528 
0.0556 


(53) 
Sp.  gr. 
0.803 
0.8105 

0.815   o 


0.8l85 
0.820 


Vis. 

0.0515 
0.0563 

0684 


0.0570 
0-0559 


45 

This  drop  in  viscosity  in  the  oils  which  occurs  at  the  bottom 
of  the  tube,  appears  to  be  a  regular  occurrence  in  the  dozen 
or  so  oils  which  have  been  tested.  Further  investigation 
of  this  point  is  intended. 

WATER  FRACTIONATION. 

To  test  the  effectiveness  of  water  fractionation  alone, 
1000  cc.  of  crude  petroleum,  previously  chilled  and  filtered, 
of  specific  gravity  0.807,  were  mixed  with  1000  gms.  of 
earth  and  allowed  to  stand  24  hours.  Water  was  then 
added  in  small  amounts  and  the  oil  collected. 

Sp.  gr.  Volume  of  oil.     Total  water  present, 

cc.  cc. 

A 0.8148  44  500 

B 0.8139  278  650 

C 0.816  211  800 

D 0.820  84  950 

E 0.8225  28  1400 

F 0.8245  28  2750 

673 

The  fractions  of  large  enough  volume  were  then  mixed 
with  earth  again  and  the  oil  replaced  with  water.  One  gram 
of  earth  was  used  for  each  cc.  of  oil,  the  earth  having  been 
heated  first  and  allowed  to  cool. 


B.  o  8139    278  cc. 
stood  1.5  hours. 

C.  0.816    211  cc. 
stood  6  hours. 

D.  0.820    84  cc. 
stood  2.5  hours. 

Sp.  gr. 

Oil. 

Water. 

Sp.  gr. 

Oil. 

Water. 

Sp.  gr.       Oil. 

Water. 

cc. 

cc. 

cc. 

0. 

8185 

IO 

70 

O 

.820 

10 

80 

0.822      32 

76 

O. 

818 

10 

1  10 

0 

.820 

20 

125 

0.823       20 

207 

0. 

818 

21 

164 

0 

.8195 

72 

250 



0. 

818 

20 

0 

.820 

30 

4IO 

52 

0. 

817 

42 

.  . 

O 

.820 

10 

588 

0. 

819 

10 

216 



0. 

820 

44 

277 

142 

0 

820 

16 

428 

0 

8215 

20 

686 

193 


46 

It  is  apparent  that  while  petroleum  is  fractionated  by 
simply  mixing  the  oil  with  fuller's  earth  and  then  displacing 
the  oil  from  the  earth  with  water,  the  fractionation  is  much 
less  complete  than  when  tubes  are  used  as  previously  de- 
scribed. 

It  will  be  noticed  that  although  fractions  C  and  D  in  the 
table  last  given  are  separated  hardly  at  all  by  further  treat- 
ment with  earth  and  water,  yet  the  specific  gravity  of  all  the 
oil  recovered  is  higher  than  that  of  the  oil  used,  e.  g.,  from 
C  of  sp.  gr.  0.816  is  obtained  nothing  lighter  than  0.8 195,  and 
from  D  of  sp.  gr.  0.820  is  obtained  nothing  lighter  than  0.822. 

To  determine  whether  the  specific  gravity  of  the  oil  re- 
covered will  continue  to  rise  after  the  oil  is  fractionated  no 
further  by  repeated  treatment,  330  cc.  of  sp.  gr.  .819,  ob- 
tained by  uniting  several  products  of  one  fractionation  of  the 
crude  petroleum,  were  mixed  with  330  grams  of  earth  and 
water  was  added. 

Sp.  gr.  Vol.  oil.       Total  water  present.  ' 

cc. 

A 6  64 

B 0.8215  50 

C .  .  12  214 

D 0.821  60'  270 

E 0.821  82  413 

F 0.8225  26  613 

236 

Seventy-five  cc.  of  E  of  sp.  gr.  0.821  were  next  mixed  with 
75  grams  of  earth  and  150  cc.  of  water  were  added.  Fifty- 
one  cc.  of  oil  whose  specific  gravity  was  unchanged,  but 
whose  color  was  reduced,  were  obtained.  Fifty  cc.  of  this 
when  treated  with  earth  and  water  returned  34  cc.  of  oil 
with  the  color  considerably  lighter,  but  the  specific  gravity 
still  0.821. 

Although  only  two-thirds  of  the  oil  used  are  recovered 
whenever  oil  is  mixed  with  earth  and  then  displaced  with 
water,  yet  this  loss  does  not  seem  to  affect  the  specific  gravity 
of  the  oil  obtained  for  longer  than  one  or  two  treatments 
after  the  oil  ceases  to  be  fractionated.  After  this  the  oil 
recovered  has  the  same  specific  gravity  as  the -oil  used. 


47 


THE  OIL  LOST  IN  THE  EARTH. 

The  sum  of  the  fractions  of  oil  displaced  from  the  earth 
is  usually  about  two-thirds  of  the  volume  of  the  oil  used. 

A  pressure  of  approximately  200  tons  per  square  inch  upon 
the  earth  from  which  water  has  displaced  all  oil  that  it  will, 
results  in  the  liberation  of  considerable  water  but  very  little 
oil.  When  earth  which  has  been  pressed  is  heated  to  165° 
for  three  hours,  considerable  water  distills  over  but  much 
less  oil  than  would  be  expected,  e.  g.,  from  75  grams  of  earth 
which  should  contain  25  cc.  of  oil,  but  4  cc.  of  oil  were  ob- 
tained. The  earth  was  removed  once  from  the  flask  and 
pulverized,  and  when  the  heat  was  discontinued  the,  earth 
was  thoroughly  dry.  On  extraction  with  ether  the  earth 
gave  a  solution  having  the  color  of  the  original  petroleum. 
The  extraction  was  made  with  a  Soxhlet  extractor  and  con- 
tinued until  the  extract  was  colorless.  On  evaporation  of 
the  ether  there  remained  about  8  cc.  of  a  heavy  oil  with  the 
color  of  the  natural  petroleum.  Pressure,  heat,  and  ex- 
traction with  ether  together  gave  about  half  the  amount  of 
oil  which  the  earth  must  have  contained. 

Earth  which  had  been  used  once  was  allowed  to  dry  for 
several  weeks  at  room  temperatures  until  it  had  lost  all 
appearance  of  containing  moisture.  It  was  then  pulverized, 
sifted,  and  used  in  a  tube  with  the  crude  petroleum  of  sp. 
gr.  0.810  with  the  following  results. 


8  cm.  at  top .  .  o 

Next  8  cm 0.8284  10 

Next  18  cm 0.8225  45 

Next  30  cm 0.8143  60 

0.8155  80 

Rest 0.8175  83 

0.819  114 

392  cc. 

Earth  used,  720  gms. 
Crude  petroleum  used,  740  cc. 


48 

The  first  oil  up  the  tube  evidently  is  absorbed  by  heavy 
material  in  the  earth,  while  the  first  oil  recovered  dissolves 
material  from  the  earth  which  increases  its  specific  gravity 
beyond  that  of  the  next  fraction. 

To  see  how  much  of  the  weight  of  the  earth  just  used  was 
due  to  material  which  it  had  retained  from  its  first  use,  300 
grams  of  earth  were  mixed  with  300  cc.  of  crude  petroleum 
and  the  oil  displaced  by  water.  The  oil  recovered  measured 
205  cc.,  and  the  weight  of  the  earth  after  drying  for  several 
weeks  at  room  temperature  was  347.5  grams.  Fully  15 
per  cent.,  therefore,  of  the  weight  of  the  earth  used  in  the 
tube  just  mentioned  was  solid  matter  which  it  had  retained 
from  its  first  use. 

In  all  cases  the  earth  was  heated  before  it  was  used  be- 
cause it  was  believed  that  heating  decreased  the  amount  of 
oil  lost  in  the  earth.  The  earth  was  heated  usually  in  iron 
pans  on  a  gas  stove  until  it  ceased  to  form  geysers  when 
stirred.  A  tube  packed  with  earth  which  had  not  been 
heated  gaye  results  as  follows  with  crude  petroleum  of  sp. 
gr.  0.810. 

Sp.  gr.  Vol. 


cc. 


Top    8  cm o .  803  30 

Next    8  cm o .  8045  38 

Next  18  cm 0.8103  &5 

Rest .  .  440 

593 
Crude  oil  used 930 

Earth  used,  948  gms. 
Tube  5  feet  long,  i  */4  inches  diameter. 
20  hours  required  at  diminished  pressure. 
In    a   case    of    water   fractionation    alone    with    unheated 
earth  but  242  cc.  of  oil  were  recovered  from  500  cc.  of  crude 
petroleum. 

Results  obtained  toward  the  close  of  our  work  indicate 
that  the  loss  of  oil  when  unheated  earth  is  used  is  much  less 
than  we  had  supposed  it  to  be.  The  gain  from  heating  the 
earth  may  not  pay  for  the  trouble  of  heating  it,  and  this 
point  should  be  investigated  before  any  very  extensive  in- 
vestigation is  again  undertaken. 


49 

Earth  after  heating  must  become  thoroughly  cold  before 
it  is  used  to  pack  tubes.  The  earth  holds  its  heat  for  several 
hours,  and  if  it  is  used  the  same  day  upon  which  it  is  heated, 
there  is  apt  to  be  contraction  in  a  tube  so  packed  sufficient 
to  allow  the  oil  to  run  up  the  side  of  the  tube  as  it  would  in  a 
vacuum. 

The  length  of  the  tubes  used  was  five  and  one-half  feet. 
A  tube  nine  feet  long  was  held  for  two  days  with  a  constant 
diminished  pressure  of  about  10  cm.  Hg,  and  connected  to 
the  same  vacuum  pump  with  several  five  and  one-half  foot 
tubes.  The  oil  was  drawn  to  the  top  of  the  latter,  and  these 
removed  and  a  second  lot  substituted  which  were  likewise 
fully  impregnated  with  oil  before  the  long  tube  was  opened. 
When  it  was  opened  the  oil  had  ascended  but  45  cm.,  showing 
that  the  diminished  pressure  had  not  penetrated  that  length 
of  earth  and  reached  the  bottom  of  the  tube. 

A  shorter  tube  in  which  the  earth  was  packed  very  much 
harder,  so  that  the  tube  filled  with  earth  rang  like  an  iron 
rod  when  pounded  upon  the  floor,  when  connected  with  a 
vacuum  pump  at  one  end  and  a  manometer  at  the  other, 
showed  diminished  pressure  on  the  manometer  when  the 
column  of  earth  was  two  feet  long  but  not  when  two  feet, 
four  inches. 

THE;  FRACTIONATING  POWER  OF  SUBSTANCES  OTHER  THAN 
FULLER'S  EARTH. 

A  clay  from  Topsham,  Maine,  was  found  which  in  tubes 
showed  a  power  of  fractionating  as  well  as  decolorizing  the 
higher  fractions.  Compared  with  fuller's  earth,  the  action 
was: 

Sp.  gr. 
Clay.  Fuller's  earth. 

8  cm.  at  top 0.799  0.793 

Next    8  cm o .  804  o .  800 

Next    8cm 0.810  0.806 

Next  10  cm. 0.810  0.807 

Next  30  cm 0.812  0.8092 

Next  45  cm 0.812  0.8112 

Time  required  69  hours,  76  hours. 

Sp.  gr.  petroleum  used,  0.806. 

Tubes  5  feet  long,  iV4  inches  in  diameter. 


50 

Neither  powdered  brick  made  from  the  same  clay  nor 
powdered  feldspar  showed  any  power  of  fractionation. 

Another  similar  clay  (from  Mere  Point,  Brunswick,  Maine) 
showed  a  power  of  water  fractionation,  but  its  behavior  in  a 
tube  was  not  tested.  400  grams  of  this  clay,  previously 
sifted  and  heated,  were  mixed  with  170  cc.  of  crude  petro- 
leum of  sp.  gr.  0.806  and  allowed  to  stand  14  hours.  Water 
was  then  added  and  the  following  fractions  obtained: 

Sp.  gr.  Vol.  in  cc.  Total  water  present. 

0.8l65  24  104 

0.817  60  133 

0.8188  20  234 

6  374 

no 
The  color  was  scarcely  changed  at  all. 


SUMMARY. 

(1)  When  petroleum  is  allowed  to  rise  in  a  tube  packed 
with  fuller's  earth,  there  is  a  decided  fractionation  of  the  oil, 
the  fraction  at  the  top  of  the  tube  being  of  lower  specific 
gravity  than  that  at  the  bottom. 

(2)  When  water  is  added  to  fuller's  earth  which  contains 
petroleum,-  the  oil  which  is  displaced  first  differs  in  specific 
gravity  from  that  which  is  displaced  afterwards  when  more 
water  is  added. 

(3)  When  petroleum  is  allowed  to  rise  in  a  tube  packed  with 
fuller's   earth,    the  paraffine  hydrocarbons  tend  to  collect  in 
the  lightest  fraction  at  the  top  of  the  tube  and  the  unsaturated 
hydrocarbons  at  the  bottom. 

(4)  Whenever  oil  is  mixed  with    fuller's    earth  and  then 
displaced   with   water,    about   one-third   of   the   oil   remains 
in  the  earth. 


BIOGRAPHY. 

Marshall  Perley  Cram  was  born  in  Brunswick,  Maine,  on 
January  i,  1882.  He  was  prepared  for  college  at  the  Bruns- 
wick High  School,  and  entered  Bowdoin  College  in  1900, 
from  which  he  was  graduated  in  1904  with  the  degree  of 
A.B.  He  was  assistant  in  chemistry  in  the  same  college  for 
the  year  1904-5  and  received  the  degree  of  A.M.  in  1905. 
Since  October,  1905,  he  has  been  a  graduate  student  in 
chemistry  in  the  Johns  Hopkins  University,  his  subordinate 
subjects  being  physical  chemistry  and  geology. 


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